Methods for fixing hair and skin

ABSTRACT

Compositions, kits, and methods for repairing bonds, for example, disulfide bonds, in hair or on the skin are disclosed. The compositions provide improved conditioning benefit for dry hair or moisturize the skin. The compositions also provide a long lasting moisturized feel and smooth feel to the skin or hair, without feeling greasy. The compositions contain one or more compounds that covalently bind at least two thiol groups in the hair or on the skin. Use of the binding compositions prevents reversion of the repaired bonds to their free thiol state, for at least one week or one month, or more, after a single application of the composition. Improved methods of styling hair, for example permanent hair waving, hair curling, hair coloring or highlighting, and hair straightening, are also provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part of PCT Application No.PCT/US2014/049388, filed Aug. 1, 2014, which is a non-provisionalapplication of U.S. Provisional Application Ser. No. 62/000,340, filedMay 19, 2014. PCT/US2014/049388 also claims also priority to U.S. patentapplication Ser. No. 14/257,056, filed Apr. 21, 2014, which is anon-provisional application of U.S. Provisional Application Ser. No.61/861,281, filed Aug. 1, 2013 and U.S. Provisional Application Ser. No.61/885,898, filed on Oct. 2, 2013. PCT/US2014/049388 also claimspriority to U.S. patent application Ser. No. 14/257,089, filed Apr. 21,2014, which is a non-provisional application of U.S. Provisionalapplication Ser. No. 61/861,281, filed Aug. 1, 2013; U.S. Provisionalapplication Ser. No. 61/867,872, filed Aug. 20, 2013; and U.S.Provisional application Ser. No. 61/903,239, filed Nov. 12, 2013.PCT/US2014/049388 also claims priority to U.S. patent application Ser.No. 14/257,076, filed Apr. 21, 2014, which is a non-provisionalapplication of U.S. Provisional Application Ser. No. 61/861,281, filedAug. 1, 2013 and U.S. Provisional Application Ser. No. 61/885,898, filedon Oct. 2, 2013. The disclosures of which are incorporated herein byreference in their entirety.

FIELD OF THE INVENTION

The present invention generally relates to compositions and methods fortreating hair or skin, particularly for repairing disulfide bonds inhair or on the skin.

BACKGROUND OF THE INVENTION

Hair consists of many long protein chains composed of amino acidbuilding blocks. These chains, or polymers, are bound to each othervia 1) hydrogen bonding, 2) salt bridges between acid and base groups,and 3) disulfide bonds. Water reversibly cleaves the hydrogen bonds.This makes wet hair easy to shape and set. When the water evaporates,hydrogen bonds form at new positions, holding the hair in this set. Instrongly acidic solutions, such as where the pH is 1.0 to 2.0, bothhydrogen bonds and salt bridges are broken. The disulfide bonds,however, can still hold the protein chains together in the strand ofhair under such conditions.

At a slightly alkaline pH of 8.5, some disulfide bonds are broken(Dombrink et al., Chem Matters, 1983, page 8). Repeated washing withslightly alkaline shampoo damages the hair by breaking more and more ofthe disulfide bonds. This causes the cuticle or outer surface of thehair strands to become ruffled and generally leaves the hair in a wet,tangled, and generally unmanageable state. This is one cause of “splitends.” Once the hair dries, it is often left in a dry, rough, or frizzycondition. Additionally, rough hair catches light unevenly and makes thehair look lusterless and dull. The hair can also be left with increasedlevels of static upon drying, which can interfere with combing andresult in a condition commonly referred to as “fly-away hair.”

Disulfide linkages are also ruptured due to heating or use of variousreducing treatments. Current compositions and methods for waving andstraightening mammalian hair use reducing agents such as thioglycolicacid, particularly as the ammonium salt, to cleave the hair's cystinedisulfide bonds. Once the disulfide bonds are broken, and the hair isplaced in stress to establish the final style (e.g., straight, wavy, orcurly) the disulfide bonds are reestablished. Oxidation to restore thereduced bonds can be achieved by simply exposing the hair to atmosphericoxygen, but this oxidation step is very slow and is of very littlepractical use. Generally, hydrogen peroxide or sodium bromate is used asthe oxidizing agent. However, the newly formed disulfide bonds are understress to maintain the hair's new shape, thus, they break easilyresulting in a reversion of the hair style over time. In addition, theuse of peroxides in the hair styling process can result in damaged hair,removal of non-natural color from the hair, and/or leave the hairfrizzy. Furthermore, some latent free thiols may remain in the hair evenafter oxidative treatment.

Treatment with peroxides used in the hair styling process results in thefollowing reaction:

2K—S—H+H₂O₂→K—S—S—K+2H₂O  (Rxn I)

where K represents keratin in the hair. However, if two K—S—H groups arenot present for the reaction (Rxn I) to take place, it is believed thatthe following reaction takes place, which results in damaged hair.

K—S—H+3H₂O₂→K—SO₂—OH+3H₂O  (Rxn II)

Keratin is also a major component in skin. Damage to the disulfidebridges of keratin can cause skin to look unhealthy or flaky.Maintaining the disulfide bridges of keratin keeps the skin healthy andprevents cracking and splitting.

A variety of approaches have been developed to alleviate these problems,including post-shampoo application of hair conditioners, such asleave-on and rinse-off products. Typically, conditioning rinses put backthe oily coating, especially to the damaged portion of the hair wherethe cuticle has become ruffled since conditioners cling best to theseportions. However, too much or too heavy a conditioner will make thehair stickier, thus attracting dirt and often may make more shampooingtreatments necessary. Typically conditioners do not bind the free thiolsin hair.

The use of cationic polymers to form coacervates to provide conditioningbenefits to the hair is known, such as described in InternationalPublished Applications WO 93/08787 to King et al. and WO 95/01152 toNapolione et al. Commonly used cationic deposition polymers includenatural polymers, such as guar gum polymers, that have been modifiedwith cationic substituents. The selection of a cationic guar polymerwith sufficient charge density and molecular weight results insufficient deposition of conditioning agents when incorporated in ashampoo or body wash. However, a relatively high level of such cationicguar polymer generally must be deposited on the hair or skin. Moreover,the cost of such cationic guar polymer is relatively high. As a result,incorporation of cationic guar polymer can increase the manufacturingcosts of such shampoo compositions. Additionally, these shampoocompositions typically are useful for wet hair conditioning, but are notcapable of delivering satisfactory dry hair smooth feel. Furthermore,these conditioners do not bind the free thiols in hair.

U.S. Pat. No. 5,656,265 to Bailey et al., discloses a hair stylingconditioning process for use after treating the hair with a reducingagent. The process involves contacting the hair with a compound havingan electrophilic group and at least one hydrophobic group. According toBailey, the electrophilic groups react with the thiol groups to providea plurality of hydrophobic groups on the hair. However, theseconditioners do not bind the free thiols in hair together.

There is a need for hair formulations and treatments that can provideimproved conditioning benefit for hair. Specifically, there is a need toprovide long lasting moisturized feel, smooth feel, and manageabilitycontrol to hair when it is dried. There is also a need for hairformulations and treatments that repair latent free thiols in the hair.

There is a need for hair formulations and treatments that repair and/orstrengthen damaged hair and rebuild stronger bonds in hair treated withreducing agents.

There is also a need for skin formulations and treatments that provideimproved conditioning and/or moisturizing benefit to the skin. Inparticular, there is a need to provide a long lasting moisturized andsmooth feel to the skin. There is also a need for skin formulations andtreatments that repair free thiols in the skin.

Therefore, it is an object of this invention to provide improvedcompositions and methods for repairing and/or strengthening damagedhair.

It is also an object of this invention to provide compositions andmethods for using these compositions that repair and/or strengthen hairafter a washing or reducing treatment.

It is also an object of this invention to provide compositions andmethods for conditioning, moisturizing, and/or otherwise treating theskin.

SUMMARY OF THE INVENTION

Compositions, kits, and methods for repairing bonds, for example,disulfide bonds, in hair or on the skin that have been damaged aredisclosed. The compositions provide improved conditioning benefit fordry hair or moisturize the skin. Specifically, the compositions providelong lasting moisturized feel and smooth feel without leaving the hairgreasy, improved appearance (e.g., sheen), increased dry strength(tensile strength), ease of combing the hair when wet or dried, lesshair breakage, and decreased frizz. The compositions also provide a longlasting moisturized feel and smooth feel to the skin.

The compositions contain one or more compounds that interact withkeratin through more than one binding events (e.g., absorption, binding,etc.) which may involve reaction with one or more thiols in the hair oron the skin. Binding herein is defined as the formation of covalent,ionic or hydrogen bonding, etc. Under normal hair washing conditions,including shampooing and conditioning, the covalent bonds formed are notsusceptible to reduction or hydrolysis. Use of the binding compositionsprevents reversion of the hair's repaired bonds to their free thiolstate, for at least one week, two weeks, three weeks, four weeks, onemonth, or two months, or longer, after application of the composition.

Improved methods of styling hair, for example permanent hair waving,hair curling, and hair straightening are also provided. The bindingcompositions can be applied each time the hair is washed or daily,once-weekly, twice-weekly, biweekly, once-monthly, every other month, orat less frequent intervals. Preferably, the binding compositions areapplied weekly or once per month to achieve the desired results.

Traditional methods of permanent hair waving, hair curling, orstraightening use hydrogen peroxide to rebuild the disulfide bonds aftera reducing treatment. The process generally takes about three days tocomplete. The methods disclosed herein use binding agents to repair thehair; these binding agents are washed from the individual's hair on thesame day that they are applied to the hair. In some embodiments, thebinding agents and the free thiol groups form a carbon-sulfur covalentbond. Under the same conditions, such as temperature and moisture, hairtreated with the binding agents takes a longer time to revert to itsprior state compared to the same hair that is untreated. The bindingagent can contain one or more reactive groups where the reactivefunctional groups are bound to the surface.

In one embodiment, the binding agent contains a linker or spacer and twoor more reactive functional groups, wherein the reactive functionalgroups are covalently bound to the linker or spacer. In otherembodiments, the binding agent contains a spacer or linker which forms asalt with the two or more reactive functional groups. In otherembodiments, the binding agent contains one or more reactive groupswhere the reactive functional groups interact with the surface of thehair or functional groups on the hair.

DETAILED DESCRIPTION OF THE INVENTION I. Definitions

The term “hair” refers to one or more than one strand of hair, as wellas the natural components of hair, such as oil from a body. Hair alsorefers to virgin hair or processed hair, for example hair that has beenexposed to hair waving or hair straightening formulations.

An “effective amount”, e.g., of the binding agent or compositionsdescribed herein, refers to an amount of the binding agent in acomposition or formulation which, when applied as part of a desireddosage regimen, binds free thiols in the hair.

“Pharmaceutically acceptable” and “cosmetically acceptable” are usedinterchangeably and refer to those compounds, materials, compositions,and/or dosage forms which are, within the scope of sound medicaljudgment, suitable for use in contact with the tissues of human beingsand animals without excessive toxicity, irritation, allergic response,or other problems or complications commensurate with a reasonablebenefit/risk ratio. More specifically, pharmaceutically acceptablerefers to a material, compound, or composition which is suitable for usein contact with the skin, scalp, or hair. Pharmaceutically acceptablematerials are known to those of ordinary skill in the art.

“Shampoo”, as used herein, generally refers to a liquid or semi-solidformulation applied to the hair that contains detergent or soap forwashing the hair.

“Conditioner”, as used herein, generally refers to a formulation (e.g.,liquid, cream, lotion, gel, semi-solid) applied to the hair to softenthe hair, smooth the hair, and/or change the sheen of the hair.

“Analog” and “Derivative” are used herein interchangeably and refer to acompound that possesses the same core as the parent compound, butdiffers from the parent compound in bond order, the absence or presenceof one or more atoms and/or groups of atoms, and combinations thereof.The derivative can differ from the parent compound, for example, in oneor more substituents present on the core, which may include one or moreatoms, functional groups, or substructures. In general, a derivative canbe imagined to be formed, at least theoretically, from the parentcompound via chemical and/or physical processes.

“Electrophilic group” or “electrophilic moiety” are used interchangeablyand refer to one or more functional groups or moieties that have anaffinity for or attract electrons.

“Michael acceptor”, as used herein, is a species of electrophilic groupsor moieties that participates in nucleophilic addition reactions. TheMichael acceptor can be or can contain an α,β-unsaturatedcarbonyl-containing group or moiety, such as a ketone. Other Michaelacceptors include pi-bonds, such as double or triple bonds conjugated toother pi-bond containing electron withdrawing groups, such as nitrogroups, nitrile groups, and carboxylic acid groups.

“Alkyl”, as used herein, refers to the radical of saturated orunsaturated aliphatic groups, including straight-chain alkyl, alkenyl,or alkynyl groups, branched-chain alkyl, alkenyl, or alkynyl groups,cycloalkyl, cycloalkenyl, or cycloalkynyl (alicyclic) groups, alkylsubstituted cycloalkyl, cycloalkenyl, or cycloalkynyl groups, andcycloalkyl substituted alkyl, alkenyl, or alkynyl groups. Unlessotherwise indicated, a straight chain or branched chain alkyl has 30 orfewer carbon atoms in its backbone (e.g., C₁-C₃₀ for straight chain,C₃-C₃₀ for branched chain), more preferably 20 or fewer carbon atoms,more preferably 12 or fewer carbon atoms, and most preferably 8 or fewercarbon atoms. In some embodiments, the chain has 1-6 carbons. Likewise,preferred cycloalkyls have from 3-10 carbon atoms in their ringstructure, and more preferably have 5, 6 or 7 carbons in the ringstructure. The ranges provided above are inclusive of all values betweenthe minimum value and the maximum value.

The term “alkyl” includes both “unsubstituted alkyls” and “substitutedalkyls”, the latter of which refers to alkyl moieties having one or moresubstituents replacing a hydrogen on one or more carbons of thehydrocarbon backbone. Such substituents include, but are not limited to,halogen, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl,or an acyl), thiocarbonyl (such as a thioester, a thioacetate, or athioformate), alkoxyl, phosphoryl, phosphate, phosphonate, aphosphinate, amino, amido, amidine, imine, cyano, nitro, azido,sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido,sulfonyl, heterocyclyl, aralkyl, or an aromatic or heteroaromaticmoiety.

Unless the number of carbons is otherwise specified, “lower alkyl” asused herein means an alkyl group, as defined above, but having from oneto ten carbons, more preferably from one to six carbon atoms in itsbackbone structure. Likewise, “lower alkenyl” and “lower alkynyl” havesimilar chain lengths. Preferred alkyl groups are lower alkyls.

The alkyl groups may also contain one or more heteroatoms within thecarbon backbone. Examples include oxygen, nitrogen, sulfur, andcombinations thereof. In certain embodiments, the alkyl group containsbetween one and four heteroatoms.

“Alkenyl” and “Alkynyl”, as used herein, refer to unsaturated aliphaticgroups containing one or more double or triple bonds analogous in length(e.g., C₂-C₃₀) and possible substitution to the alkyl groups describedabove.

“Aryl”, as used herein, refers to 5-, 6- and 7-membered aromatic rings.The ring may be a carbocyclic, heterocyclic, fused carbocyclic, fusedheterocyclic, bicarbocyclic, or biheterocyclic ring system, optionallysubstituted as described above for alkyl. Broadly defined, “Ar”, as usedherein, includes 5-, 6- and 7-membered single-ring aromatic groups thatmay include from zero to four heteroatoms. Examples include, but are notlimited to, benzene, pyrrole, furan, thiophene, imidazole, oxazole,thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine andpyrimidine. Those aryl groups having heteroatoms in the ring structuremay also be referred to as “heteroaryl”, “aryl heterocycles”, or“heteroaromatics”. The aromatic ring can be substituted at one or morering positions with such substituents as described above, for example,halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl,alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate,phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl,sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic orheteroaromatic moieties, perfluoroalkyl, and cyano. The term “Ar” alsoincludes polycyclic ring systems having two or more cyclic rings inwhich two or more carbons are common to two adjoining rings (the ringsare “fused rings”) wherein at least one of the rings is aromatic, e.g.,the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls,aryls and/or heterocycles, or both rings are aromatic.

“Alkylaryl”, as used herein, refers to an alkyl group substituted withan aryl group (e.g., an aromatic or hetero aromatic group).

“Heterocycle” or “heterocyclic”, as used herein, refers to a cyclicradical attached via a ring carbon or nitrogen of a monocyclic orbicyclic ring containing 3-10 ring atoms, and preferably from 5-6 ringatoms, containing carbon and one to four heteroatoms each selected fromnon-peroxide oxygen, sulfur, and N(Y) wherein Y is absent or is H, O,(C₁₋₄) alkyl, phenyl or benzyl, and optionally containing one or moredouble or triple bonds, and optionally substituted with one or moresubstituents. The term “heterocycle” also encompasses substituted andunsubstituted heteroaryl rings. Examples of heterocyclic ring include,but are not limited to, benzimidazolyl, benzofuranyl, benzothiofuranyl,benzothiophenyl, benzoxazolyl, benzoxazolinyl, benzthiazolyl,benztriazolyl, benztetrazolyl, benzisoxazolyl, benzisothiazolyl,benzimidazolinyl, carbazolyl, 4aH-carbazolyl, carbolinyl, chromanyl,chromenyl, cinnolinyl, decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl,dihydrofuro[2,3-b]tetrahydrofuranyl, furanyl, furazanyl, imidazolidinyl,imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl,indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl,isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl,isothiazolyl, isoxazolyl, methylenedioxyphenyl, morpholinyl,naphthyridinyl, octahydroisoquinolinyl, oxadiazolyl, 1,2,3-oxadiazolyl,1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl,oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl,phenazinyl, phenothiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl,piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl,pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl,pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole,pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl,pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl,quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl,tetrahydroquinolinyl, tetrazolyl, 6H-1,2,5-thiadiazinyl,1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl,1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl,thienooxazolyl, thienoimidazolyl, thiophenyl and xanthenyl.

“Heteroaryl”, as used herein, refers to a monocyclic aromatic ringcontaining five or six ring atoms containing carbon and 1, 2, 3, or 4heteroatoms each selected from non-peroxide oxygen, sulfur, and N(Y)where Y is absent or is H, O, (C₁-C₈) alkyl, phenyl or benzyl.Non-limiting examples of heteroaryl groups include furyl, imidazolyl,triazolyl, triazinyl, oxazoyl, isoxazoyl, thiazolyl, isothiazoyl,pyrazolyl, pyrrolyl, pyrazinyl, tetrazolyl, pyridyl, (or its N-oxide),thienyl, pyrimidinyl (or its N-oxide), indolyl, isoquinolyl (or itsN-oxide), quinolyl (or its N-oxide) and the like. The term “heteroaryl”can include radicals of an ortho-fused bicyclic heterocycle of abouteight to ten ring atoms derived therefrom, particularly abenz-derivative or one derived by fusing a propylene, trimethylene, ortetramethylene diradical thereto. Examples of heteroaryl include, butare not limited to, furyl, imidazolyl, triazolyl, triazinyl, oxazoyl,isoxazoyl, thiazolyl, isothiazoyl, pyraxolyl, pyrrolyl, pyrazinyl,tetrazolyl, pyridyl (or its N-oxide), thienyl, pyrimidinyl (or itsN-oxide), indolyl, isoquinolyl (or its N-oxide), quinolyl (or itsN-oxide), and the like.

“Halogen”, as used herein, refers to fluorine, chlorine, bromine, oriodine.

The term “substituted” as used herein, refers to all permissiblesubstituents of the compounds described herein. In the broadest sense,the permissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and nonaromaticsubstituents of organic compounds. Illustrative substituents include,but are not limited to, halogens, hydroxyl groups, or any other organicgroupings containing any number of carbon atoms, preferably 1-14 carbonatoms, and optionally include one or more heteroatoms such as oxygen,sulfur, or nitrogen grouping in linear, branched, or cyclic structuralformats. Representative substituents include alkyl, substituted alkyl,alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, phenyl,substituted phenyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, halo, hydroxyl, alkoxy, substituted alkoxy, phenoxy,substituted phenoxy, aroxy, substituted aroxy, alkylthio, substitutedalkylthio, phenylthio, substituted phenylthio, arylthio, substitutedarylthio, cyano, isocyano, substituted isocyano, carbonyl, substitutedcarbonyl, carboxyl, substituted carboxyl, amino, substituted amino,amido, substituted amido, sulfonyl, substituted sulfonyl, sulfonic acid,phosphoryl, substituted phosphoryl, phosphonyl, substituted phosphonyl,polyaryl, substituted polyaryl, C₃-C₂₀ cyclic, substituted C₃-C₂₀cyclic, heterocyclic, substituted heterocyclic, aminoacid, peptide, andpolypeptide groups.

Heteroatoms, such as nitrogen, may have hydrogen substituents and/or anypermissible substituents of organic compounds described herein thatsatisfy the valences of the heteroatoms. It is understood that“substitution” or “substituted” includes the implicit proviso that suchsubstitution is in accordance with permitted valence of the substitutedatom and the substituent, and that the substitution results in a stablecompound, i.e. a compound that does not spontaneously undergotransformation such as by rearrangement, cyclization, elimination, etc.

“Polymer”, as used herein, refers to a molecule containing more than 10monomer units.

“Water-soluble”, as used herein, generally means at least 10, 50, 100,125, 150, 200, 225, or 250 g is soluble in 1 L of water at 25° C.

“Binding agent”, as used herein, means as used herein, refers to amolecule that forms covalent, ionic or hydrogen bonding, etc. with thehair and generally includes the formation of at least one covalent bondwith a free thiol.

II. Binding Formulations

The formulations disclosed herein are concerned with treating hair orskin. In particular, the formulations can rebuild latent disulfide bondsin hair or skin. Additionally, the formulations may also react with freeamines in the hair to provide a conditioning effect.

The formulations contain one or more binding agents (also referred toherein as “compounds” or “active agents”).

The binding agents can be combined with one or more pharmaceuticallyacceptable carriers and/or excipients that are considered safe andeffective to human hair, skin, and/or human scalp, and may beadministered to an individual's hair without causing undesirable sideeffects, such as burning, itching, and/or redness, or similar adversereactions. The formulations may further contain an excipient thatrenders the formulations neutral pH, or a pH ranging from about pH 3 toabout pH 12, preferably from pH 5 to pH 8.

The binding agent is typically present in an amount ranging from about0.01 wt % to about 50 wt % of the formulation, preferably from aboutfrom about 1 wt % to about 25 wt % of the formulation, more preferablyfrom about 1 wt % to about 15 wt %, most preferably from about 1 wt % toabout 10 wt %. Typically, the binding agent is about 2.5-3 wt % of theformulation.

The binding agent is stable in aqueous solution for a period of at least2, 3, 4, 5, 6, 8, 9, 10, 11, or 12 months or longer at pH of 6 to 8 anda temperature of about 25-30° C., preferably about 25° C. “Stable” asused herein with respect to shelf-life means that at least 40, 45, 50,55, 60, 65, 70, 75, 80, 85, 90, or 95% of the reactive moieties areintact or to the extent that the reactive moieties react with water, theresulting product is also electrophilic.

a. Binding Agent

The binding agent contains at least two reactive moieties capable ofreacting with a thiol. The binding agent optionally contains a linkerbetween the two or more reactive moieties. The linker forms two or moreionic bonds with the reactive moieties. The reactive moieties, uponreaction with thiol groups on the hair follicle, form bonds that arestable, for example, hydrolytically stable. “Stable”, as used inreference to the bonds formed between thiol groups on hair folliclesmeans the bonds remain intact for at least one week, two weeks, threeweeks, four weeks, one month, or two months or longer when exposed towater at pH 6-8 at a temperature from about 5° C. to about 100° C.,preferably from about 20° C. to about 75° C., more preferably from about20° C. to about 50° C., more preferably from about 25° C. to about 40°C., most preferably from about 25° C. to about 30° C. In someembodiments, the temperature is about 25° C. It is also preferred thatthe binding reaction occur around room temperature, for example, fromabout 15° C. to about 35° C., preferably from about 20° C. to about 30°C., more preferably from about 22° C. to about 27° C.

The binding agents typically have a low molecular weight and arecompatible with aqueous or solvent delivery systems. In someembodiments, the compound is water-soluble. The low molecular weight ispreferred, as it allows the molecule to diffuse in and out of hair at areasonable rate. Molecular weights of less than 10,000 Da, 8,000 Da,6,000 Da, 5,000 Da, 4,000 Da, 3,000 Da, 2,000 Da, or 1,000 Da arepreferred. In some embodiments, the molecular weight is less than 1500Da, preferably less than 800 Da, most preferably less than 500 Daltonsto achieve sufficient diffusion rates in conventional aqueous hair caresystems.

i. Binding Agents Defined by Formula I

In some embodiments, the binding agents have a structure according toFormula I:

wherein

A, B, C, and D are reactive moieties containing one or more charges,

R is a linker that contains two or more charges, wherein the charges areopposite to the charges on the reactive moieties,

and

each occurrence of p, q, r, and s is independently an integer from 0 to25, preferably from 0 to 10, more preferably from 0 to 2. The sum ofp+q+r+s is equal to or greater than 2.

The reactive moieties may be present on any atom of the linker. In someembodiments, the reactive moieties are the same. In some embodiments,one or more of the reactive moieties is different.

In some embodiments, the reactive moieties are negatively charged andthe linker or spacer has positively charged moieties. In otherembodiments, the reactive moieties are positively charged and the linkeror spacer has negatively charged moieties. Generally, the sum of thecharges on the binding agent of Formula I is zero though stoichiometricimbalances may exist.

ii. Linker

The reactive moieties on the binding agents are preferably linked via alinker. The term “linker”, as used herein, refers to one or morepolyfunctional, e.g. bifunctional molecules, trifunctional molecules,tetrafunctional molecules, etc., which can be used to ionically boundthe two or more reactive moieties and which do not interfere with thereactive properties of the binding agents. The reactive moieties may beattached to any part of the linker.

Linkers can be a single atom, such as a heteroatom (e.g., O or S), agroup of atoms, such as a functional group (e.g., amine, —C(═O)—,—CH₂—), or multiple groups of atoms, such as an alkylene chain. Suitablelinkers include but are not limited to oxygen, sulfur, carbon, boron,nitrogen, alkoxy, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl,heterocycloalkyl, heteroaryl, ether, amine, and a polymer.

The linker is optionally independently substituted with one or moresubstituents including hydrogen, halogen, cyano, alkoxy, alkyl, alkenyl,cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, amine,hydroxy, formyl, acyl, carboxylic acid (—COOH), —C(O)R¹, —C(O)OR¹,carboxylate (—COO⁻), primary amide (e.g., —CONH₂), secondary amide(e.g., —CONHR¹), —C(O)NR¹R², —NR¹R², —NR¹S(O)₂R², —NR¹C(O)R², —S(O)₂R²,—SR¹, and —S(O)₂NR¹R², sulfinyl group (e.g., —SOR¹), and sulfonyl group(e.g., —SOOR¹); wherein R¹ and R² may each independently be hydrogen,alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyl andheteroaryl; wherein each of R¹ and R² is optionally independentlysubstituted with one or more substituents selected from the groupconsisting of halogen, hydroxyl, cyano, nitro, amino, alkylamino,dialkylamino, alkyl optionally substituted with one or more halogen oralkoxy or aryloxy, aryl optionally substituted with one or more halogenor alkoxy or alkyl or trihaloalkyl, heterocycloalkyl optionallysubstituted with aryl or heteroaryl or ═O or alkyl optionallysubstituted with hydroxyl, cycloalkyl optionally substituted withhydroxyl, heteroaryl optionally substituted with one or more halogen oralkoxy or alkyl or trihaloalkyl, haloalkyl, hydroxyalkyl, carboxy,alkoxy, aryloxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl anddialkylaminocarbonyl.

In some embodiments, the linker may be an alkoxy, ether, alkyl, alkenyl,cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, amine, ora polymer. In some embodiments, the linker is not a polymer.

iii. Polymeric Binding Agents

The binding agent can be a polymer. In this form, the linker forms or isthe polymer backbone having ionically associated therewith two or morereactive moieties. Optionally, the polymeric binding agent can have astructure according to Formula I. In some forms, for each occurrence ofa monomer unit in the polymer, zero, one, two, three, four, or morereactive moieties can be ionically associated with, the monomer. Thereactive moieties on each monomer unit in the polymer can be the same ordifferent.

In some embodiments, at least one reactive moiety is present on eachmonomer unit. Alternately, the reactive moieties may be present onalternate monomer units. In some embodiments, reactive moieties arepresent on a minimum percentage of the monomer units in the polymer. Forexample, at least one reactive moiety can be present on 0.1%, 1%, 5%,10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%,80%, 85%, 90%, 95%, or 100% of the monomer units in the polymer. Thereactive moieties can be present on any atom on the monomer.

Polymers

The polymer may be functionalized at the termini (and/or within thepolymer backbone) with one or more of reactive moieties, A-D. One ormore monomers in the polymer may be functionalized so that one or morereactive moieties, A-D, may be introduced (e.g., ionically associatedwith) using techniques known in the art. For ionically associatedmoieties, the salt is typically generated in situ.

A wide variety of polymers and methods for forming the polymers areknown in the art of polymer science. Polymers can be degradable ornon-degradable polymers. Polymers can be natural or unnatural(synthetic) polymers. Polymers can be homopolymers or copolymerscomprising two or more monomers. In terms of sequence, copolymers can berandom, block, or comprise a combination of random and block sequences.The polymers can in some embodiments be linear polymers, branchedpolymers, or hyperbranched/dendritic polymers. The polymers may also bepresent as a bound particle or surface functionalized inorganicparticle. Suitable polymers include, but are not limited to poly (vinylacetate), copolymers of styrene and alkyl acrylates, and copolymers ofvinyl acetate and acrylic acid, polyvinylpyrrolidone, dextran,carboxymethylcellulose, polyethylene glycol, polyalkylene,polyacrylates, and polymethacrylates; polyanhydrides; polyorthoesters;polystyrene (PS), poly(ethylene-co-maleic anhydride), poly(ethylenemaleic anhydride-co-L-dopamine), poly(ethylene maleicanhydride-co-phenylalanine), poly(ethylene maleicanhydride-co-tyrosine), poly(butadiene-co-maleic anhydride),poly(butadiene maleic anhydride-co-L-dopamine) (pBMAD), poly(butadienemaleic anhydride-co-phenylalanine), poly(butadiene maleicanhydride-co-tyrosine), poly(bis carboxy phenoxy propane-co-sebacicanhydride) (poly (CCP:SA)), alginate; and poly(fumaricanhydride-co-sebacic anhydride (p[FA:SA]), copolymers of p[FA:SA],polyacrylates and polyacrylamides, and copolymers thereof, andcombinations thereof. In some embodiments, the polymeric linker ispreferably water-soluble.

For polymeric linkers, the number of monomers is typically greater thanor equal to 1, such as 1-10 (e.g., oligomer) or greater than 10 (e.g.,polymer), such as 10-1000 or greater.

iv. Reactive Moieties that React with Thiols

The binding agent contains at least two reactive moieties that reactwith thiols to form covalent bonds. The reactive moieties are capable ofreacting with a thiol group in the hair or on the skin to form a stablecovalent bond. The reactive moiety is typically an electrophilic moietycapable of forming a salt with the linker. Alternately, the reactivemoiety can be a free radical forming moiety.

The binding agent contains at least two reactive moieties. However, thebinding agent may contain three, four, five, six, or greater than sixreactive moieties.

The reaction between the reactive moiety and the thiol groups may beinitiated at room temperature and pressure when the reactive moietycontacts a thiol group in the hair or on the skin. In some embodiments,the reaction may require an initiator, such as heat, catalyst, basicconditions, or a free radical initiator. The rate of reaction betweenthe reactive moiety and the thiol may be increased by changes intemperature, pH, and/or addition of one or more excipients, such as acatalyst; however, this is generally not required.

The two or more reactive moieties on the binding agent can be the same.In some embodiments, the two or more reactive moieties are different.

In some embodiments, the reactive moieties are capable of undergoing aconjugate additional reaction. The reactive moieties can independentlybe or contain a Michael acceptor, a succinimidyl-containing group, amaleimido-containing group, azlactone, a benzoxazinone derivative, vinylsulfone, vinyl sulfoximine, vinyl sulfonate, vinyl phosphonate,benzoxazinone, isocyanate, epoxide, an electrophilic moiety containing aleaving group, an electrophilic thiol acceptor, acrylic or acrylategroup, a methacrylic or methacrylate group, a styrene group, an acrylamide group, a methacryl amide group, a maleate group, a fumarate group,an itaconate group, a vinyl ether group, an allyl ether group, an allylester group, a vinyl ester group, a sulfonate group, a phosphonategroup, a sulfoxide group, a sulfonamide group, a sulfinimide group, asulfinamide group, a sulfonimidate group, or a sulfonimidamide group.

Michael Acceptor

A “Michael acceptor,” as used herein, is a compound or moiety with atleast one Michael acceptor functional group with the structure below:

Where E is —C(═O)R₃, —C(═O)OR₃, —C(═O)NHR₃, —CN, —S(O)R₃ or —S(O)₂R₃,where R₃, R₄, R₅, and R₆ taken independently, are hydrogen or a group orgrouping selected from, but not limited to, alkyl, substituted alkyl,alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, phenyl,substituted phenyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, halo, hydroxyl, alkoxy, substituted alkoxy, phenoxy,substituted phenoxy, aroxy, substituted aroxy, alkylthio, substitutedalkylthio, phenylthio, substituted phenylthio, arylthio, substitutedarylthio, cyano, isocyano, substituted isocyano, carbonyl, substitutedcarbonyl, carboxyl, substituted carboxyl, amino, substituted amino,amido, substituted amido, sulfonyl, substituted sulfonyl, sulfonic acid,phosphoryl, substituted phosphoryl, phosphonyl, substituted phosphonyl,polyaryl, substituted polyaryl, C3-C20 cyclic, substituted C3-C20cyclic, heterocyclic, substituted heterocyclic, aminoacid, peptide, andpolypeptide groups. In certain embodiments, R₃ and one of R₄, R₅, or R₆may together form a ring.

Some suitable Michael acceptors include, but are not limited tomolecules in which some or all of the structure above are residues of(meth)acrylic acid, fumaric acid, or maleic acid, substituted versionsthereof, or combinations thereof, attached to the Michael acceptormolecule through an ester linkage.

The linker is attached to the Michael acceptor via R₃, R₄, R₅, or R₆. Insome embodiments, R₃, R₄, R₅, or R₆ may be the linker

Vinyl Sulfone

The chemistry of vinyl sulfones with respect to attack by nucleophilesis analogous to that of α,β-unsaturated ketones in that they can undergoa 1,4-type Michael addition without releasing any undesirableby-products.

Vinyl Sulfoximines

The chemistry of vinyl sulfoximines is similar to vinyl sulfones. TheN-tosyl sulfoximine group is more electron withdrawing than the phenylsulfone and therefore the vinyl groups will be more susceptible towardsnucleophilic attack. N-substituents can be used to alter theelectrophilic potential of the vinyl group.

Electrophilic Moiety Containing a Leaving Group

The reactive moiety may be an electrophile with a leaving group.Electrophile, as used herein refers to one or more functional groups ormoieties that have an affinity for or attract electrons. Suitableelectrophiles include, but are not limited to, ester moieties(—(CO)—O—R, wherein R is lower alkyl or the like), carbonyl moieties(—C(O)), carboxylic acid or carbonic acid (—COOH or —OCOOH), carbonatemoieties (—O—(CO)—O—R, wherein R is lower alkyl or the like), urethanemoieties (—O—(CO)—NH—R, wherein R is H, lower alkyl, or the like),substituted urethane moieties (—O—(CO)—NR′—R, where R′ is a nonhydrogensubstituent such as alkyl, aryl, alkaryl, or the like), amido moieties(—(CO)—NH—R, wherein R is H, lower alkyl, or the like), substitutedamido moieties (—(CO)—NR′—R where R′ is as defined previously),thioester moieties (—(CO)—S—R, wherein R is H, lower alkyl, or thelike), sulfonic ester moieties (—S(O)₂—O—R, wherein R is H, lower alkyl,or the like), and the like. Other electrophiles will be known to thoseof ordinary skill in the art of organic chemistry and polymer scienceand/or can be readily found by reference to the pertinent texts andliterature.

The electrophiles preferably contain a leaving group. Suitable leavinggroups are well known in the art, see, e.g., “Advanced OrganicChemistry,” Jerry March, 5th Ed., pp. 445-448, John Wiley and Sons, N.Y.Examples of leaving groups include, but are not limited to, halogen,sulfonyloxy, optionally substituted alkylsulfonyloxy, optionallysubstituted alkenylsulfonyloxy, optionally substituted arylsulfonyloxy.Specific examples of leaving groups include chloro, iodo, bromo, fluoro,methanesulfonyloxy (mesyloxy), tosyloxy, triflyloxy,nitrophenylsulfonyloxy (nosyloxy), bromophenylsulfonyloxy (brosyloxy),hydroxyl, carboxylate, carbonate, phosphate, phosphonate, phosphinate,phosphonium, urethane, urea, amide, imide, amine, ammonium, sulfonato,—N₃, CN, RO—, NH₂O—, NHRO—, N(R⁴)₂O—, R⁴CO₂—, R⁴OCO₂—, R⁴NCO₂—, R⁴S—,R⁴C(S)O—, R⁴CS₂—, R⁴SC(O)S—, R⁴SCS₂— R⁴SCO₂—, R⁴OC(S)O—, R⁴OCS₂—,R⁴SO₂—, R⁴SO₃—, R⁴OSO₂—, R⁴OSO₃—, R⁴PO₃—, R⁴OPO₃—, an N-imidazolylgroup, an N-triazolyl group, an N-benzotriazolyl group, abenzotriazolyloxy group, an imidazolyloxy group, an N-imidazolinonegroup, an N-imidazolone group, an N-imidazolinethione group, anN-imidazolinethione group, an N-succinimidyl group, an N-phthalimidylgroup, an N-succinimidyloxy group, an N-phthalimidyloxy group,—ON═C(CN)R⁴, and a 2-pyridyloxy group. R⁴ is preferably an alkyl groupor an aryl group.

Preferably, the leaving group is removed from the reactive moieties anddoes not result in the formation of side product that disadvantageouslyaffects the reaction between the reactive moieties and the thiol groupsor form a material or compound that is unsuitable for contact with skinor hair.

In some embodiments, the leaving group is a halogen.

Electrophilic Thiol Acceptors

Electrophilic thiol acceptors, as used herein, refer to a chemicalmoiety that reacts with a thiol group so that the sulfur atom of thethiol group becomes covalently bonded to the thiol acceptor. Thiolacceptors are well known in the art. Koval (Reactions of Thiols, RussianJournal of Organic Chemistry, 2007, 43:319-349) discloses severalelectrophilic thiol acceptors, the disclosure of which is incorporatedherein by reference.

Electrophilic thiol acceptors, in addition to those listed above,include but are not limited to an alpha-substituted acetyl group withthe formula Y—CH₂—CO— wherein Y is a leaving group. Examples of leavinggroups include, but are not limited to, chloride, bromide, iodide,mesylate, tosylate, and the like. If the thiol acceptor is analpha-substituted acetyl group, the thiol adduct after covalent linkageto the acceptor forms the bond —S—CH₂—.

Free Radical-Forming Groups

The binding agent may contain at least two free radical-forming groupsthat can react with thiols. The free radical-forming groups on thebinding agent can be the same. Alternately, the free radical-forminggroups may be different. Suitable free radical forming groups include,but are not limited to acrylate groups, methacrylate groups, styrenegroups, acryl amide groups, methacryl amide groups, maleate groups,fumarate groups, itaconate groups, vinyl ether groups, allyl ethergroups, allyl ester groups, and vinyl ester groups. For example,suitable binding agents include ethylene glycol dimethacrylate,diethylene glycol diacrylate, allyl methacrylate, trimethylolpropanetriacrylate, triallylamine, tetraallyloxyethane, and di- andtriacrylates, mixed acrylates which, as well as acrylate groups,comprise further ethylenically unsaturated groups. Other examples ofbinding agents include N,N′-methylenebisacrylamide andN,N′-methylenebismethacrylamide, esters of unsaturated mono- orpolycarboxylic acids of polyols, such as diacrylate or triacrylate, forexample butanediol diacrylate, butanediol dimethacrylate, ethyleneglycol diacrylate, ethylene glycol dimethacrylate and alsotrimethylolpropane triacrylate and allyl compounds, such as allyl(meth)acrylate, triallyl cyanurate, diallyl maleate, polyallyl esters,tetraallyloxyethane, triallylamine, tetraallylethylenediamine, allylesters of phosphoric acid and also vinylphosphonic acid derivatives,pentaerythritol diallyl ether, pentaerythritol triallyl ether,pentaerythritol tetraallyl ether, polyethylene glycol diallyl ether,ethylene glycol diallyl ether, glycerol diallyl ether, glycerol triallylether, polyallyl ethers based on sorbitol, and also ethoxylated variantsthereof. Other examples of binding agents include di- and triacrylatesof 3- to 15-tuply ethoxylated glycerol, of 3- to 15-tuply ethoxylatedtrimethylolpropane, of 3- to 15-tuply ethoxylated trimethylolethane,especially di- and triacrylates of 2- to 6-tuply ethoxylated glycerol orof 2- to 6-tuply ethoxylated trimethylolpropane, of 3-tuply propoxylatedglycerol, of 3-tuply propoxylated trimethylolpropane, and also of3-tuply mixed ethoxylated or propoxylated glycerol, of 3-tuply mixedethoxylated or propoxylated trimethylolpropane, of 15-tuply ethoxylatedglycerol, of 15-tuply ethoxylated trimethylolpropane, of 40-tuplyethoxylated glycerol, of 40-tuply ethoxylated trimethylolethane and alsoof 40-tuply ethoxylated trimethylolpropane, ethylene glycoldimethacrylate, diethylene glycol diacrylate, allyl methacrylate,trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane,N,N′-methylenebisacrylamide, N,N′-methylenebismethacrylamide, butanedioldiacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate,triallyl cyanurate, diallyl maleate, a polyallyl ester,tetraallylethylenediamine, pentaerythritol diallyl ether,pentaerthyritol triallyl ether, pentaerythritol tetraallyl ether,polyethylene glycol diallyl ether, ethylene glycol diallyl ether,glycerol diallyl ether, glycerol triallyl ether, di- and triacrylates of3- to 15-tuply ethoxylated glycerol, di- and tri-acrylates of 3- to15-tuply ethoxylated trimethylolpropane, and di- and tri-acrylates of 3-to 15-tuply ethoxylated trimethylolethane. As used herein, the term“tuply” refers to the number of monomeric units in the ethoxylatedchain.

The reactive free radical moieties may require the presence of one ormore initiators. Suitable initiators include, but are not limited toperoxides, hydroperoxides, hydrogen peroxide, persulfates, azocompounds, and redox initiators. Suitable organic peroxides includeacetylacetone peroxide, methyl ethyl ketone peroxide, tert-butylhydroperoxide, cumene hydroperoxide, tert-amyl perpivalate, tert-butylperpivalate, tert-butyl perneohexanoate, tert-butyl perisobutyrate,tert-butyl per-2-ethylhexanoate, tert-butyl perisononanoate, tert-butylpermaleate, tert-butyl perbenzoate, di(2-ethylhexyl) peroxydicarbonate,dicyclohexyl peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, dimyristil peroxydicarbonate, diacetylperoxydicarbonate, allyl peresters, cumyl peroxyneodecanoate, tert-butylper-3,5,5-trimethylhexanoate, acetylcyclohexylsulfonyl peroxide,dilauryl peroxide, dibenzoyl peroxide, and tert-aryl perneodecanoate.Suitable azo compounds include 2,2′-azobisisobutyronitrile,2,2′-azobis(2,4-dimethylvaleronitrile) and2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), preferablywater-soluble azo initiators, such as, but not limited to,2,2′-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride,2,2′-azobis-(2-amidinopropane)dihydrochloride,2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride and2,2′-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride. Forthe redox initiators, the oxidizing component is at least one of theperoxo compounds indicated above and the reducing component is, forexample, ascorbic acid, glucose, sorbose, ammonium bisulfite, ammoniumsulfite, ammonium thiosulfate, ammonium hyposulfite, ammoniumpyrosulfite, ammonium sulfide, alkali metal bisulfite, alkali metalsulfite, alkali metal thiosulfate, alkali metal hyposulfite, alkalimetal pyrosulfite, alkali metal sulfide, or sodiumhydroxymethylsulfoxylate.

In some embodiments, the molecule is:

In some embodiments, the binding agent has the structure:

The reaction with thiol groups on hair follicles is as follows:

Other agents include, but are not limited to, acid-containingelectrophiles, such as acrylic acid and bromo-acetic acid and similarcompounds.

b. Excipients

The formulations typically contain one or more cosmetically acceptableexcipients. Cosmetically acceptable excipients include, but are notlimited to, water, preservatives, antioxidants, chelating agents,sunscreen agents, vitamins, dyes, hair coloring agents, proteins, aminoacids, natural extracts such as plant extracts, humectants, fragrances,perfumes, oils, emollients, lubricants, butters, penetrants, thickeners,viscosity modifiers, polymers, resins, hair fixatives, film formers,surfactants, detergents, emulsifiers, opacifying agents, volatiles,propellants, liquid vehicles, carriers, salts, pH adjusting agents(e.g., citric acid), neutralizing agents, buffers, hair conditioningagents, anti-static agents, anti-frizz agents, anti-dandruff agents,absorbents, and combinations thereof.

The formulations can contain at least two or more cosmeticallyacceptable excipients. In some forms, the formulations contain thebinding agent, water, and optionally a preservative and/or fragrance.

The formulation for treating hair may be in any suitable physical form.Suitable forms include, but are not limited to low to moderate viscosityliquids, lotions, milks, mousses, sprays, gels, creams, shampoos,conditioners, and the like. Suitable excipients, such as those listedabove, are included or excluded from the hair care formulation dependingon the form of use of the formulation (e.g., hair spray, cream,conditioner, or shampoo).

The formulation for treating skin may be in any suitable physical form.Suitable forms include, but are not limited to low to moderate viscosityliquids, lotions, milks, mousses, sprays, gels, creams, ointments, andthe like. Suitable excipients, such as those listed above, are includedor excluded from the skin formulation depending on the form of use ofthe formulation (e.g., lotion, gel, ointment, or cream).

The pharmaceutical excipient is typically present in an amount rangingfrom about 10 wt % to about 99.99 wt % of the formulation, preferablyabout 40 wt % to about 99 wt %, more preferably from about 80 wt % toabout to about 99 wt %.

i. Surfactants

Surfactants are surface-active agents that are able to reduce thesurface tension of water and cause the formulation to slip across oronto the skin or hair. Surfactants also include detergents and soap. Thesurfactants may be amphoteric, anionic, or cationic. Suitablesurfactants that may be used in the formulation include, but are notlimited to, 3-aminopropane sulfonic acid, almond amide, almondamidopropyl betaine, almond amidopropylamine oxide, aluminumhydrogenated tallow glutamate, aluminum lanolate, aminoethyl sulfate,aminopropyl lauryl glutamine, ammonium C₁₂₋₁₅ alkyl sulfate, ammoniumC₁₂₋₁₅ pareth sulfate, ammonium C₁₂₋₁₆ alkyl sulfate, ammonium C₉₋₁₀perfluoroalkylsulfonate, ammonium capryleth sulfate, ammoniumcapryleth-3 sulfate, ammonium monoglyceride sulfate, ammonium sulfate,ammonium isothionate, ammonium cocoyl sarcosinate, ammonium cumenesulfonate, ammonium dimethicone copolyol sulfate, ammoniumdodecylbenzenesulfonate, ammonium isostearate, ammonium laureth sulfate,ammonium laureth-12 sulfate, ammonium laureth-5 sulfate, ammoniumlaureth-6 carboxylate, ammonium laureth-7 sulfate, ammonium laureth-8carboxylate, ammonium laureth-9 sulfate, ammonium lauroyl sarcosinate,ammonium lauryl sulfate, ammonium lauryl sulfosuccinate, ammonium myrethsulfate, ammonium myristyl sulfate, ammonium nonoxynol-30 sulfate,ammonium nonoxynol-4 sulfate, ammonium oleate, ammonium palm kernelsulfate, ammonium polyacrylate, ammonium stearate, ammonium tallate,ammonium xylene sulfonate, ammonium xylene sulfonate, amp-isostearoylgelatin/keratin amino acids/lysine hydroxypropyltrimonium chloride,amp-isostearoyl hydrolyzed collagen, apricot kernel oil PEG-6 esters,apricot amide, apricot amidopropyl betaine, arachideth-20, avocadamide,avocadamidopropyl betaine, babassuamide, babassuamidopropyl betaine,babassuamidopropylamine oxide, behenalkonium chloride, behenamide,behenamide, behenamidopropyl betaine, behenamine oxide, sodium laurethsulfate, sodium lauryl sulfate, a polyoxyether of lauryl alcohol orceteareth-20, or combinations thereof.

Suitable anionic surfactants include, but are not limited to, thosecontaining carboxylate, sulfonate and sulfate ions. Examples of anionicsurfactants include sodium, potassium, ammonium of long chain alkylsulfonates and alkyl aryl sulfonates such as sodium dodecylbenzenesulfonate; dialkyl sodium sulfosuccinates, such as sodium dodecylbenzenesulfonate; dialkyl sodium sulfosuccinates, such as sodiumbis-(2-ethylthioxyl)-sulfosuccinate; and alkyl sulfates such as sodiumlauryl sulfate. Cationic surfactants include, but are not limited to,quaternary ammonium compounds such as benzalkonium chloride,benzethonium chloride, cetrimonium bromide, stearyl dimethylbenzylammonium chloride, polyoxyethylene and coconut amine. Examples ofnonionic surfactants include ethylene glycol mono stearate, propyleneglycol myristate, glyceryl monostearate, glyceryl stearate,polyglyceryl-4-oleate, sorbitan acylate, sucrose acylate, PEG-150laurate, PEG-400 monolaurate, polyoxyethylene monolaurate, polysorbates,polyoxyethylene octylphenylether, PEG-1000 cetyl ether, polyoxyethylenetridecyl ether, polypropylene glycol butyl ether, Poloxamer 401,stearoyl monoisopropanolamide, and polyoxyethylene hydrogenated tallowamide. Examples of amphoteric surfactants include sodiumN-dodecyl-.beta.-alanine, sodium N-lauryl-β-iminodipropionate,myristoamphoacetate, lauryl betaine and lauryl sulfobetaine.

More than one surfactant may be included in the formulation.

The surfactants are optionally included in an amount ranging from about0.1% to about 15% by weight of the formulation, preferably about 1% toabout 10% by weight of the formulation.

ii. Emollients

Emollient refers to a material that protects against wetness orirritation, softens, soothes, coats, lubricates, moisturizes, protects,and/or cleanses the skin. Suitable emollients for use in theformulations include, but are not limited to a silicone compound (e.g.,dimethicone, cyclomethicone, dimethicone copolyol or a mixture ofcyclopentasiloxane and dimethicone/vinyldimethicone cross polymer,cyclopentasiloxane polysilicone), polyols such as sorbitol, glycerin,propylene glycol, ethylene glycol, polyethylene glycol, caprylyl glycol,polypropylene glycol, 1,3-butane diol, hexylene glycol, isoprene glycol,xylitol; ethylhexyl palmitate; a triglyceride such as caprylic/caprictriglyceride and fatty acid ester such as cetearyl isononanoate or cetylpalmitate. In a specific embodiment, the emollient is dimethicone,amidodimethicone, dimethiconol, cyclopentasiloxane, potassiumdimethicone PEG-7 panthenyl phosphate, or a combination thereof. Morethan one emollient may be included in the formulation.

The emollient is optionally included in an amount ranging from about0.5% to about 15% by weight of the formulation, preferably from about 1%to about 10% by weight of the formulation.

iii. Emulsifiers

The formulations may also contain one or more emulsifiers. Suitableemulsifiers include, but are not limited to, copolymers of anunsaturated ester and styrene sulfonate monomer, cetearyl alcohol,glyceryl ester, polyoxyethylene glycol ether of cetearyl alcohol,stearic acid, polysorbate-20, ceteareth-20, lecithin, glycol stearate,polysorbate-60, or polysorbate-80, or combinations thereof. More thanone emulsifier may be included in the formulation.

The emulsifier is optionally included in an amount ranging from about0.05% to about 15% by weight of the formulation, preferably from about0.1% to about 10% by weight of the formulation.

iv. Preservatives

One or more preservatives may be included in the formulations to preventmicrobial growth in the formulations. Suitable preservatives include,but are not limited to, glycerin containing compounds (e.g., glycerin orethylhexylglycerin or phenoxyethanol), benzyl alcohol, parabens(methylparaben, ethylparaben, propylparaben, butylparaben,isobutylparaben, etc.), sodium benzoate, ethylenediamine-tetraaceticacid (EDTA), potassium sorbate, and/or grapefruit seed extract, orcombinations thereof. More than one preservative may be included in theformulation. Other preservatives are known in the cosmetics industriesand include salicylic acid, DMDM Hydantoin, Formaldahyde, Chlorphenism,Triclosan, Imidazolidinyl Urea, Diazolidinyl Urea, Sorbic Acid,Methylisothiazolinone, Sodium Dehydroacetate, Dehydroacetic Acid,Quaternium-15, Stearalkonium Chloride, Zinc Pyrithione, SodiumMetabisulfite, 2-Bromo-2-Nitropropane, Chlorhexidine Digluconate,Polyaminopropyl biguanide, Benzalkonium Chloride, Sodium Sulfite, SodiumSalicylate, Citric Acid, Neem Oil, Essential Oils (various), LacticAcid, and Vitamin E (tocopherol).

The preservative is optionally included in an amount ranging from about0.1% to about 5% by weight of the formulation, preferably from about0.3% to about 3% by weight of the formulation. Preferably, theformulations are paraben free.

v. Conditioning Agents

One or more conditioning agents may be included in the formulations.Suitable conditioning agents include, but are not limited to,silicone-based agents (e.g., silicone quaternium-8), panthenol,hydrolyzed wheat and/or soy protein, amino acids (e.g. wheat aminoacids), rice bran wax, meadowfoam seed oil, mango seed oil, grape seedoil, jojoba seed oil, sweet almond oil, hydroxyethyl behenamidopropyldimonium chloride, aloe leaf extract, aloe barbadensis leaf juice,phytantriol, panthenol, retinyl palmitate, behentrimonium methosulfate,cyclopentasiloxane, quaternium-91, stearamidopropyl dimethylamine, andcombinations thereof.

The conditioning agent(s) is optionally included in an amount rangingfrom about 0.1% to about 5% by weight of the formulation, preferablyfrom about 0.3% to about 3% by weight of the formulation.

vi. Diluents

Diluent, as used herein, refers to a substance(s) that dilutes thebinding agent. Water is the preferred diluent. The formulationstypically contains greater than one percent (wt) water, preferablygreater than five percent (wt) water, more preferably greater than 50%(wt) water, and most preferably greater than 80% (wt)water. Alcohols,such as ethyl alcohol and isopropyl alcohol, may be used at lowconcentrations (about 0.5% by weight of the formulation) to enhance hairor skin penetration and/or reduce odor.

vii. Viscosity Modifying Agents

The formulations may contain one or more viscosity modifying agents,such as viscosity increasing agents. Classes of such agents include, butare not limited to, viscous liquids, such as polyethylene glycol,semisynthetic polymers, such as semisynthetic cellulose derivatives,synthetic polymers, such as carbomers, poloxamers, andpolyethyleneimines (e.g., PEI-10), naturally occurring polymers, such asacacia, tragacanth, alginates (e.g., sodium alginate), carrageenan,vegetable gums, such as xanthan gum, petroleum jelly, waxes, particulateassociate colloids, such as bentonite, colloidal silicon dioxide, andmicrocrystalline cellulose, surfactants, such as PPG-2 hydroxyethylcoco/isostearamide, emulsifiers, such as disteareth-75 IPDI, and salts,such as sodium chloride, and combinations thereof.

viii. Antioxidants

The formulations may contain one or more antioxidants. Examples include,but are not limited to, tocopheryls, BHT, ascorbic acid, camelliasinensis leaf extract, ascorbyl palmitate, magnesium ascorbyl phosphate,carotenoids, resveratrol, triethyl citrate, arbutin, kojic acid,tetrahexydecyl ascorbate, superoxide dismutase, zinc, sodiummetabisulfite, lycopene, ubiquinone, and combinations thereof

ix. Opacifying Agents

The formulations may contain one or more opacifying agents. Opacifyingagents are added to the formulations to make them opaque. Suitableopacifying agents include, but are not limited to, glycol distearate andethoxylated fatty alcohols.

c. Forms of the Formulation

i. Sprays

The formulation may be in the form of a spray. The spray typicallyincludes the binding agent and a cosmetically acceptable carrier. Insome embodiments, the carrier is water or a water and alcohol mixture.The spray formulation optionally includes an antioxidant, sunscreenagent, vitamin, protein, peptide, plant extract, humectant, oil,emollient, lubricant, thickener, hair conditioning agent, polymer,and/or surfactant. Preferably, the spray formulation includes apreservative. In some embodiments, the formulation includes a fragrance.In some embodiments, the formulation includes a surfactant. In someembodiments, the formulation contains water, fragrance, a preservative,and a binding agent. In some embodiments, the formulation containswater, fragrance, a preservative, and a binding agent. In someembodiments, the formulation contains water, a preservative, fragrance,the binding agent, and an anti-static agent. In some embodiments, theformulation contains water, a preservative, fragrance, the bindingagent, and a hair conditioning agent. In some embodiments, theformulation contains water, a preservative, fragrance, the bindingagent, and a surfactant.

The hair spray formulations may be dispensed from containers thatinclude aerosol dispensers or pump spray dispensers. Such dispensers areknown in the art and are commercially available from a variety ofmanufacturers.

Propellant

When the hair spray formulation is dispensed from a pressurized aerosolcontainer, a propellant may be used to force the composition out of thecontainer. Suitable propellants include, but are not limited to, aliquefiable gas or a halogenated propellant. Examples of suitablepropellants include dimethyl ether and hydrocarbon propellants such aspropane, n-butane, iso-butane, CFCs, and CFC-replacement propellants.The propellants may be used singly or admixed.

The amount of propellant may range from about 10% to about 60% by weightof the formulation. The propellant may be separated from the hair repairformulation as in a two compartment container. Other suitable aerosoldispensers are those characterized by the propellant being compressedair, which can be filled into the dispenser using a pump or equivalentdevice prior to use. Conventional non-aerosol pump spray dispensers,i.e., atomizers, may also be used to apply the hair strengtheningformulation to the hair.

ii. Conditioners

The formulation may be in the form of a conditioner. The conditionertypically includes the binding agent in a suitable carrier.Additionally, the conditioner may include cationic polymers derived frompolysaccharides, for example cationic cellulose derivatives, cationicstarch derivatives, cationic guar derivatives and cationic locust beangum derivatives, synthetic cationic polymers, mixtures or combinationsof these agents. The formulation may comprise other synthetic or naturalpolymers or polymers derived from biological preparation processes,which are functionalized, where appropriate, for example with cationicor neutral groups. These polymers may have a stabilizing orstrengthening action on the compositions, and/or a conditioning action(deposition on the surface of the skin or the hair).

The binding agent may be included in any suitable concentration. Typicalconcentrations of the binding agent in the conditioner range from smallamounts such as approximately 0.01% (wt), preferably at least 0.1% (wt),to large amounts, such as up to 50% (wt). Preferably the conditionercontains the binding agent in a concentration ranging from 0.1% (wt) to5% (wt), more preferably from 0.1% wt to 3% (wt). While greaterconcentrations of binding agent could be present in the conditioner,they are generally not needed to achieve the desired results.

iii. Shampoos

The hair repair formulation may be in the form of a shampoo. The shampootypically includes the binding agent in a suitable carrier. The bindingagent may be included in any suitable concentration. Typicalconcentrations of the binding agent in the shampoo range from smallamounts such as approximately 0.01% (wt), preferably at least 0.1% (wt),to large amounts, such as up to 50% (wt). Preferably the shampoocontains the binding agent in a concentration ranging from 0.1% (wt) to5% (wt), more preferably from 0.1% wt to 3% (wt). While greaterconcentrations of binding agent could be present in the shampoo, theyare generally not needed to achieve the desired results.

Additionally, the shampoo may include from about 0.5% to about 20% of asurfactant material. Surfactants utilized in shampoo compositions arewell-known in the art and are disclosed, for example, in U.S. Pat. No.6,706,258 to Gallagher et al. and U.S. Pat. No. 7,598,213 to Geary etal.

iv. Creams

The formulation may be in the form of a cream. The cream typicallyincludes the binding agent in a suitable carrier. The binding agent maybe included in any suitable concentration. Typical concentrations of thebinding agent in the cream range from small amounts such asapproximately 0.01% (wt), preferably at least 0.1% (wt), to largeamounts, such as up to 50% (wt). Preferably the cream contains thebinding agent in a concentration ranging from 0.1% (wt) to 5% (wt), morepreferably from 0.1% wt to 3% (wt). While greater concentrations ofbinding agent could be present in the cream, they are generally notneeded to achieve the desired results.

Additionally, the cream may include an oil, a hair conditioning agent,and/or a thickening agent. The cream may also include a fragrance, aplant extract, and/or a surfactant. The cream may be packaged in a tube,tub, bottle, or other suitable container.

v. Liquid Binding Formulations

In some embodiments, a liquid binding formulation is provided, which ismixed at the time of use with a second formulation, such as a coloringor highlighting formulation. In these embodiments, the liquid bindingformulation may contain any suitable concentration of binding agent in asuitable carrier, typically a diluent, such as described above. Theconcentration of the binding agent is suitable to provide a mixture withthe appropriate final volume and final concentration of binding agent.

For example, a liquid binding formulation can contain a concentration ofbinding agent ranging from about 5% (wt) to about 50% (wt) or greater.In a preferred embodiment, the liquid binding formulation contains about20% (wt) binding agent.

The terms “highlighting” and “bleaching” are used synonymously herein.For highlighting applications, prior to use, a sufficient volume of aliquid binding formulation is mixed with a sufficient volume of ahighlighting formulation to form a highlighting mixture having thedesired concentration of binding agent. Typical concentrations of thebinding agent in the highlighting mixture range from small amounts, suchas approximately at least 0.01% (wt), preferably at least 0.1% (wt), tolarge amounts, such as up to 50% (wt). Preferably the highlightingmixture contains the binding agent in a concentration ranging from 0.1%(wt) to 5% (wt), more preferably from 0.1% wt to 3% (wt). While greaterconcentrations of binding agent could be present in the highlightingmixture, they are generally not needed to achieve the desired results.

Alternatively, two separate formulations are applied, such as a firstformulation containing bleach (i.e. the highlighting formulation), and asecond formulation containing a binding agent (i.e. the bindingformulation) in an effective amount to covalently bind the free thiolgroups. The highlighting formulation may be applied first, whichproduces free thiol groups in hair. Subsequently, the second bindingformulation may be applied to bind the free thiol groups.

III. Kit

Kits for treating hair typically contain a binding formulationcontaining an effective amount of a binding agent to covalently bindlatent free thiol groups in hair.

Instructions for use of the kit are also typically provided.

The kit may further contain a formulation, also referred to herein asthe reducing formulation, capable of reducing the disulfide bonds in thehair and producing free thiol groups.

a. Reducing Formulation

The first formulation may be a reducing formulation. A reducingformulation contains a reducing agent capable of reducing the disulfidebonds in hair and producing free thiol groups. The reducing formulationmay differ depending on the hair styling treatment desired (such as hairwaving or hair straightening), the texture of the hair, the sensitivityof the user's skin, and the like.

Formulations containing reducing agents and their selection are wellknown to those skilled in the cosmetic industry. Suitable reducingagents include, but are not limited to, thioglycolic acid andthioglycolic acid salts and esters, thiolactic acid and thiolactic acidsalts and esters, cysteine thioglycerol, thioglycolic hydrazide,thioglycolamide, glycerol monothioglycolate, sodium metabisulfite,beta-mercaptopropionic acid, N-hydroxyethyl mercapto-acetamide, N-methylmercapto-acetamide, beta-mercapto-ethylamine, beta-mercaptopropionamide,2-mercapto-ethanesulfonic acid, dimercaptoadipic acid, dithiothreitol,homocysteinethiolactone, cysteine derivatives, polythiol derivativesformed by the addition of cysteamine onto a maleicanhydride-alkylvinylether copolymer, inorganic sulfites, inorganicbisulfites, cysteamine and its derivatives, dithioerythritol, organicphosphines, and Japanese relaxers.

In some embodiments, the kit contains a reducing formulation, whichcontains a reducing agent for permanent hair waving and hair curlingsuch as acid perms, alkaline perms, perms having neutral pH, or permsusing buffered alkaline waving lotions. Such reducing agents include,but are not limited to thioglycolic acid and its derivative salts andesters, thiolactic acid and its derivative salts and esters, cysteineand its derivatives, cysteamine and its derivatives, inorganic sulfites,and inorganic bisulfites such as sodium metabisulfite, dithiothreitol,dithioerythritol, organic phosphines, and Japanese relaxers.

In other embodiments, the kit contains a reducing formulation, whichcontains a reducing agent for straightening hair. Such reducing agentsinclude, but are not limited, to inorganic bisulfites such as sodiummetabisulfite, inorganic sulfites, and ammonium thioglycolate,dithiothreitol, dithioerythritol, organic phosphines, and Japaneserelaxers.

The amount of the reducing agent in the reducing formulation issufficient to rupture a sufficient number of disulfide bonds foreffective hair waving, hair curling, or hair straightening as would beappreciated by one of skill in the art.

b. Coloring Formulation

The first formulation may be a coloring treatment. The first formulationmay be formulated as two or more components may be mixed together beforeapplication to the hair. For example, the first formulation may be inthe form of two components such as a dye precursor and an oxidant.Typically, the hair coloring formulation contains a reducing agentcapable of reducing the disulfide bonds in hair and producing free thiolgroups. Suitable reducing agents include, but are not limited to,thioglycolic acid, thiolactic acid, dihydrolipoate, thioglycerol,mercaptopropionic acid, sodium bisulfite, ammonium bisulfide, zincformaldehyde sulfoxylate, sodium formaldehyde sulfoxylate, sodiummetabisulfite, potassium borohydride, pegylated thiols and hydroquinone.The amount of the reducing agent in the first formulation is sufficientto rupture a sufficient number of disulfide bonds for effectivediffusion of the hair coloring ingredients as would be appreciated byone of skill in the art.

The components of the first formulation may differ depending on the haircoloring treatment desired (such as for semi-permanent, demi-permanent,or permanent hair color), the texture of the hair, the sensitivity ofthe user's skin, and such the like. Hair coloring formulations fordifferent hair coloring treatment, hair texture, and hair sensitivityare known to those of skill in the art.

c. Binding Formulation

The binding formulation contains an effective amount of a binding agentto bind free thiols in the hair. Suitable formulations containing thebinding agents are discussed above. The binding formulation may be inany suitable form. Suitable forms include, but are not limited to, lowto moderate viscosity liquids, lotions, milks, mousses, sprays, gels,creams, shampoos, conditioners, and the like. The binding formulationwill be present in a suitable container, which depends on the form ofthe formulation.

In one embodiment, the binding formulation is provided as two or moreseparate ingredients. For example, the binding agent may be provided asa dry powder in a sealed package and the excipient provided in a vial orother container. A suitable mixing container for the binding agent andthe excipient may be provided.

Optionally, the binding agent is premixed with a shampoo or conditioner.

In some embodiments, the binding formulation (or second formulation) ismixed with the first formulation (reducing formulation or hair coloringtreatment), and the mixture is applied to the hair.

c. Other Materials in the Kit

The kit optionally contains shampoos and conditioners. Suitable shampoosand conditioners include, but are not limited to LiQWd® HydratingShampoo and LiQWd® Hydrating Conditioner.

The kit may further contain an odor eliminator. The odor eliminator canbe incorporated into the reducing formulation. Alternately, the odoreliminator is present in a suitable container for use before or afterwashing the binding formulation from the hair. Some suitable odoreliminators are known to those of ordinary skill in the art.

IV. Methods of Use

The methods disclosed herein are concerned with treating hair with freethiol groups.

A. Treating Damaged Hair with Free Thiol Groups

In one embodiment, prior to treatment with a binding agent, the hair hasbeen damaged and the thiol groups in the hair are free thiols. Thebinding agent can be applied to the hair to bind the free thiol groups.Preferably, the binding agent is applied at least within one week of thehair being damaged, preferably within three days, more preferably withintwo days, most preferably, the same day.

a. Rinse or Wash the Hair

Optionally, the hair may be shampooed and/or conditioned prior toapplying the binding formulation. Alternately, the hair may only berinsed with water prior to application of the binding formulation.

b. Apply the Binding Formulation to the Hair

Subsequent to shampooing, conditioning, and/or rinsing the hair, thebinding formulation is applied to the hair. Alternately, the hair doesnot have to be washed or rinsed prior to application of the bindingformulation. In this embodiment, the binding formulation is applied todry hair.

The binding formulations may be used as a daily conditioning treatmentfor hair.

Typically, the amount of binding formulation applied is sufficient tosaturate the hair.

The binding formulation may be applied to the hair as a singleapplication, or application of the binding agent may be repeated one ormore times. Typically, the amount of binding formulation applied in eachapplication is sufficient to saturate the hair. The volume of bindingformulation applied to the hair in each application may be about 1 toabout 100 mL per person depending on their length and volume of hair. Insome embodiments, application of the binding agent could be repeatedimmediately (e.g. within about 10 to 15 seconds) or between about oneand five minutes, greater than five minutes, between about five and tenminutes, greater than ten minutes, between about ten and twenty (20)minutes after the first application.

c. Remove the Binding Formulation from the Hair

Preferably, the hair is washed or rinsed subsequent to the applicationof the binding formulation. The hair may be rinsed and subsequentlywashed immediately (e.g. within 10, 15, 25, 30, 45, 60 seconds (oneminute), two minutes, three minutes, four, or five minutes followingapplication) after final application of the binding agent. Alternativelythe hair may be rinsed and washed about within about 30 minutesfollowing application, preferably between about 5 minutes and about 20minutes, more preferably about 10 minutes after the final application ofthe binding agent to the hair, depending on the hair type.

Alternately, the hair does not have to be washed or rinsed subsequent toapplication of the binding formulation.

The binding agent covalently binds latent free thiols in the hair. Thethiols remain bound for at least one week, preferably for at least onemonth following application of the binding agent. The thiols may remainbound for longer periods of time, such as for about two months or morefollowing application of the binding agent. The binding reaction is astable reaction, such that the thiols may remain bound even if subjectedto a hair coloring treatment (simultaneous or subsequent to the bindingreaction).

B. Chemical Treatment of Hair with a Reducing Agent

In one embodiment, prior to treatment with a binding agent, the hair hasbeen subjected to a reducing agent used for waving (also referred toherein as hair perming or permanent waves), curling, and/orstraightening of the hair.

a. Apply a Reducing Agent to the Hair

The first step in waving, curling, or straightening hair is breaking thecysteine disulfide bonds to form free thiol moieties. The process forbreaking the cysteine disulfide bonds is via application of a reducingagent. The process for applying the reducing agent involves followingnormal perming or hair straightening procedures, that are known to thoseskilled in the art. For example, to perm a hair, the hair is firstwashed and set on perm rods of various sizes. Second, a reducing agent,such as thioglycolate reducing solution or lotion, is applied to thehair. The hair is allowed to set for a specified period of time, andthen the thioglycolate solution is rinsed from the hair.

The application of hydrogen peroxide in this process is optional. Insome processes, such as when treating previously chemically treatedhair, hydrogen peroxide is generally not used. In other processes, suchas when perming virgin hair, hydrogen peroxide may be added. In theseembodiments, hydrogen peroxide is typically added after the reducingagent is rinsed out. Then the hydrogen peroxide is rinsed from the hairprior to adding the binding agent.

b. Apply the Binding Agent

Subsequent to the reducing treatment, one or more of the binding agent,or a formulation thereof is applied to the hair. Although the bindingagent is typically applied on the same day as treatment with thereducing agent, it may be applied later, such as within 1 to 2 weeksfollowing treatment with the reducing agent.

Typically, the amount of binding formulation applied is sufficient tosaturate the hair. The binding agent is generally rinsed and shampooedfrom the hair after the desired level of hair waving, curling, orstraightening is achieved. In some embodiments, the binding agent isrinsed from the hair immediately (e.g. within 10, 15, 25, 30, 45, or 60seconds following application) following the final application of thebinding agent. Alternatively the hair may be rinsed and washed aboutwithin about 30 minutes following application, preferably between about5 minutes and about 20 minutes, more preferably about 10 minutes afterthe final application of the binding agent to the hair, depending on thehair type. The binding agent can be rinsed from the hair within 10, 15,25, 30, 45, 60 seconds from the hair after application, and stillachieve a desired level of hair waving, curling, or straightening

The binding agent may be applied to the hair as a single application, orapplication of the binding agent may be repeated one or more times.Typically, the amount of binding formulation applied in each applicationis sufficient to saturate the hair. In some embodiments, the volume ofbinding formulation applied to the hair in each application is about 1to about 10 mL per perm rod. In some embodiments, application of thebinding agent could be repeated immediately (e.g. within 10 to 15seconds) or approximately 1, 5, 7.5, 10, 12.5, 15, 17.5, or 20 minutesafter the first application. In some embodiments, the second applicationis about 7 minutes to about 10 minutes after the first application.

The binding agent is rinsed from the hair after its application. Thehair may be rinsed and washed immediately (e.g. within 10 to 15 secondsfollowing application) after final application of the binding agent.Alternatively the hair may be rinsed and washed about 10 minutes orlater after the final application of the binding agent, such as about 15minutes to about 30 minutes, preferably about 20 minutes after repeatedapplication of the binding agent to the hair.

The binding agent covalently binds the free thiols in the hair. Thethiols remain bound for at least one week, two weeks, three weeks, fourweeks, one month, two months or more.

The binding agents are generally washed from the individual's hair onthe same day as they are applied. In contrast, traditional perms whichuse only hydrogen peroxide (and do not involve the addition of across-linking agent) are generally not washed for at least 48 hoursfollowing application (washing the hair prior to 48 hours following atraditional permanent treatment may result in significant loss in theamount of curl in the hair and/or cause damage to the hair).

The compositions described herein improve hair quality, such asappearance (e.g., sheen) and feel, increase dry strength (e.g., tensilestrength), and decrease hair breakage when the hair is subjected tosubsequent treatments, such as coloring.

In some embodiments, hair breakage decreases by 5, 10, 15, 20, 25, 30,35, 40, 45, 50, 55, 60, 65, 70, or 75% or higher after treatment withthe binding agent compared to untreated hair from the same individual.Hair breakage is a significant problem encountered during coloring andother treatments.

C. Apply the Coloring Formulation to the Hair

The coloring formulation is generally applied to an individual's hairfollowing normal hair coloring procedures that are known to thoseskilled in the art. Typically, hair color treatments include twocomplementary processes: bleaching the hair's natural pigment and/orother artificial pigments present in the hair, and diffusion of dyeprecursors into the hair, followed by coupling reactions that result inthe formation of chromophores within the hair shaft, which are too largeto diffuse out of the hair. The hair coloring formulation may be ahighlighting formulation, such as formed by mixing bleach powder anddeveloper. More complex colors may contain several precursors and manycouplers, and may involve multiple reactions.

The dye precursors may contain several ingredients, each with differentfunctions. The first ingredient is usually an alkalizing agent (usuallyammonia and/or an ammonia substitute, such as monoethanolamine [MEA]).The alkalizing agent serves a number of roles in the hair colorantprocess including swelling the hair fiber to aid in diffusion of the dyeprecursors. The dye precursors generally include p-diamines andp-aminophenols. Precursors are oxidized to active intermediates oncethey have penetrated the hair shaft. Intermediates then react with colorcouplers to create wash resistant dyes. More specifically, theintermediates, in the presence of an oxidant, couple with anotheroxidation dye intermediate molecule to form a large fused ring colorcompound within the hair shaft. The precursor intermediate shouldpenetrate the hair shaft prior to the coupling reaction since the fusedring product is too large to penetrate the hair shaft. Couplers modifythe color produced by the oxidation of precursor compounds. The primarydifference between demi-permanent and permanent products is thealkalizing agent and the concentration of peroxide. The cuticle does notswell as greatly with demi-permanent dyes, making dye penetration lessefficient compared to permanent coloring products.

Several coloring formulations use a reducing agent, such as sodiumbisulfate, to break disulfide bonds in the hair, allowing deeperpenetration of the hair coloring dyes into the hair. Specifically, themethod includes reducing some of the disulfide linkages of the cysteinein the hair shafts to thiol groups while breaking hydrogen bonds. Thereducing process changes the chemical and cosmetic characteristics ofthe hair, which are undesirable.

The hair dyeing process may be followed by a shampoo and conditioningtreatment, a neutralizing rinse or an acid balanced shampoo containingin addition to cationic or amphoteric surfactants, cation-activeemollients and quarternary polymers. Alternately, the hair dyeingprocess may be followed by application of the binding formulationsdescribed herein, before a shampoo and/or conditioning treatment.

a. Applying Binding Formulation

The binding formulation may be applied simultaneously with the haircoloring formulation or subsequently to the application of the haircoloring formulation. For example, the binding formulation may be mixedwith the hair coloring treatment and the mixture, containing both thebinding formulation the hair coloring treatment, may be applied to thehair.

Alternatively, subsequent to coloring the hair, the binding formulation,or a formulation thereof is applied to the hair. Although the bindingagent is typically applied on the same day as the coloring treatment, itmay be applied later such as within 1 to 2 weeks following treatmentwith the reducing agent. Typically, the amount of binding formulation(or a mixture of the binding formulation and the hair coloringformulation) applied is enough to saturate the hair. The bindingformulation may be applied to the hair as a single application, orapplication of the binding agent may be repeated one or more times.Typically, the amount of binding formulation applied in each applicationis sufficient to saturate the hair. The volume of binding formulationapplied to the hair in each application may be about 1 to about 100 mLper person depending on their length and volume of hair. In someembodiments, application of the binding agent could be repeatedimmediately (e.g. within 10 to 15 seconds) or approximately 1, 5, 7.5,10, 12.5, 15, 17.5, or 20 minutes after the first application.

The binding agent can be rinsed and shampooed from the hair immediatelyfollowing application, for example within 10, 15, 25, 30, 45, or 60seconds, or two, three, four, or five minutes after application.Alternatively, the binding agent may be rinsed from the hair withinabout 30 minutes following application, preferably between about 5minutes and about 20 minutes, more preferably about 10 minutes afterapplication of the binding agent to the hair, depending on hair type.

If the binding formulation is combined with the hair coloring treatmentand applied as a mixture to the hair, then the mixture remains on thehair as long as needed for the hair coloring treatment. Typically themixture is applied for approximately 10 minutes. The mixture is removedfrom the hair in accordance with standard methods for hair coloringtreatments, e.g., rinse and shampoo, approximately 10 minutes afterapplying the mixture.

The binding formulation is rinsed from the hair after its application.The hair may be rinsed and subsequently washed immediately (e.g. within10 to 15 seconds following application) after final application of thebinding agent. Preferably, the hair is rinsed and/or washed about 10minutes or later after the final application of the binding agent, suchas about 15 minutes to about 30 minutes, optionally about 20 minutesafter repeated application of the binding agent to the hair.

The binding agent covalently binds the free thiols in the hair. Thethiols remain bound for at least one week, two weeks, three weeks, fourweeks, one month, or two months, or more.

The binding agents are generally washed from the individual's hair onthe same day as they are applied. In contrast, traditional perms whichuse only hydrogen peroxide (and do not involve the addition of across-linking agent) are generally not washed for at least 48 hoursfollowing application (washing the hair prior to 48 hours following atraditional permanent treatment may result in significant loss in theamount of curl in the hair and/or cause damage to the hair).

The compositions described herein improve hair quality, such asappearance (e.g., sheen) and feel, increase dry strength (e.g., tensilestrength), and decrease hair breakage when the hair is subjected tosubsequent treatments, such as coloring.

In some embodiments, hair breakage decreases by 5, 10, 15, 20, 25, 30,35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% or higher aftertreatment with the binding agent compared to untreated hair from thesame individual. Hair breakage is a significant problem encounteredduring coloring and other treatments.

EXAMPLES Example 1 Comparison of Traditional Perm Versus Perm UsingBismaleate Binding Agent

General Hair samples were obtained from a human subject and cut in ½inch wide wefts.

Reducing Agents:

Ammonium thioglycolate (ATG) was obtained from a permanent wave kitmanufactured by Zotos. 300 mg of Dithiothreitol in a 10 g solution wasalso used as the reducing agent.

Binding Formulation:

A bismaleate binding agent2,2′-(ethane-1,2-diylbis(oxy))bis(ethan-1-amine)di-maleate at aconcentration of 300 mg in 10 g total solution (water) was used.

Methods

Method for Perming Hair Using the Binding Agents

The hair was washed with clarifying shampoo, towel dried, and thenrolled around a perm rod. Ammonium thioglycolate or dithiothreitol wasthen applied to the hair and left on the hair for 10 minutes to 1 hour.The hair was then rinsed for 30 seconds to 1 minute and then blotted drywith a towel.

The binding formulation was applied to the hair, via a needle noseapplicator, drenching the hair. The binding agent was left on the hairfor a period of about 7.5 minutes. The hair was drenched for a secondtime with the binding formulation and left for a second 7.5 minutes, fora total of 15 minutes. The hair was then rinsed with water for about 1-2minutes then unrolled from the perm rods. After the hair was removedfrom the perm rods, the hair was shampooed and conditioned with varioussalon shampoo and conditioner brands, including LiQWd® Hydrating Shampooand Hydrating Conditioner. The washing and drying steps were repeated 40times.

A second portion of hair was permed as described above, except, hydrogenperoxide was used instead of the binding formulation.

Results

Both perms (utilizing the binding formulation or hydrogen peroxide)showed only slight reduction in the overall curl after 40 cycles ofwashing and drying with the same shampoo and conditioner. However, theappearance and texture of the perm using the binding formulation showedmore sheen and less fizz compared to the perm using hydrogen peroxide.

Example 2 Comparison of Hair Breakage Due to Repeated Application ofTraditional Perm and the Binding Formulations

Methods

Two hair samples were obtained. Both samples were treated withdithiothreitol or ammonium thioglycolate as described in Example 1. Oneof the hair samples was subsequently treated with the bindingformulation, while the other was neutralized with hydrogen peroxide. Theprocess was completed the same day for the hair treated with the bindingformulation. The process was completed in three days with hydrogenperoxide (traditional perm).

The procedure was repeated three times for each hair sample over a 48hour time period.

Results

Upon visual inspections, the second hair sample treated with the bindingformulation showed little or no signs of breakage. However, the firsthair sample treated with hydrogen peroxide showed significant breakage.

Example 3 Comparison of the Extent of Damage to Hair Previously Relaxedwith a Japanese Relaxer

Methods

Two samples of hair, the first previously straightened with a Japaneserelaxer (Yuko), and the second previously straightened with a no lyerelaxer (African Pride Miracle Deep Conditioning) were obtained. Thesamples were treated as described in Examples 1 and 2 using the bindingformulation.

Another hair sample, previously straightened with a no lye relaxer(African Pride Miracle Deep Conditioning) was obtained. The sample wastreated with a traditional hair straightening perm (Zotos).

Results

The hair samples treated with the binding formulation showed nonoticeable damage. However, the sample treated with a traditional permshowed significant breaking, even during application.

Example 4 Hair Sheen and Texture after Treatment with BindingFormulation

General

A sample of untreated virgin gray hair was obtained from a humansubject.

Binding Formulation:

The bismaleate binding agent in Example 1 (300 mg) was dissolved inwater (10 g). The resulting solution was mixed with LiQWD VolumizingConditioner® in a 1:1 ratio.

Methods

A section of the virgin gray hair was washed with LiQWD® HydratingShampoo and then blotted dry with a towel. The hair was then combed witha wide tooth comb followed by combing with a fine tooth comb for 2minutes.

After combing, the binding formulation (about 4 mL) was applied to thehair sample by hand and then the sample combed through for approximately1 minute. The hair sample was left undisturbed for a period of about 10minutes, after which it was rinsed with water, and then washed withLiQWD® Volumizing Shampoo and Conditioner before being examined.

The hair sample was washed and conditioned for an additional five (5)times with LiQWD® Volumizing Shampoo and Conditioner.

A second section of the virgin gray hair, the control, was treatedidentically as above, except the binding formulation was not applied tothe control hair sample. Thus after the hair was combed, LiQWDVolumizing Conditioner® (without a binding agent) was applied to thehair sample by hand.

Results:

The hair sample treated with the binding formulation had more shine andfelt softer to the touch that the original untreated sample. The treatedhair sample gave an overall healthier appearance compared to the controlsample.

The shine, texture, and overall appearance remained intact after fiveshampoo and conditioning treatments.

Example 5 Hair Sheen and Texture after Treatment with BindingFormulation

General

A sample of untreated virgin blonde hair described as highly porous anddifficult to comb through was obtained from a human subject.

Binding Formulation:

The bismaleate binding agent in Example 1 (300 mg) was dissolved inwater (10 g). The resulting solution was mixed with LiQWD EnhancingConditioner® in a 1:1 ratio.

Methods

A section of the virgin blonde hair was washed with LiQWD® HydratingShampoo and then blotted dry with a towel. The hair was then combed witha wide tooth comb followed by combing with a fine tooth comb for 5minutes.

The binding formulation (about 7 mL) was then applied to the hair sampleby hand and the sample combed through for approximately 2 minutes. Thehair sample was left undisturbed for a period of about 5 minutes afterwhich the hair was treated again with the binding formulation (about 4mL). The hair sample was combed through for approximately 10 seconds andleft undisturbed for about 5 minutes.

The hair sample was then rinsed with water then washed with LiQWD®Sulfate Free Enhancing Shampoo and Conditioner before examination.

Following initial examination, the sample was washed and conditioned foran additional two (2) times with LiQWD® Sulfate Free Enhancing Shampooand Conditioner.

A second section of the virgin blonde hair, the control, was treatedidentically as above, except the binding formulation was not applied tothe control hair sample. Thus, after the hair was combed, LiQWDVolumizing Conditioner® (without a binding agent) was applied to thehair sample by hand.

Results:

The hair sample treated with the binding formulation had more shine andfelt softer to the touch than the original untreated sample. The treatedhair sample gave an overall healthier appearance compared to the controlsample.

The shine, texture, and overall appearance remained intact after twoshampoo and conditioning treatments.

Example 6 Color Retention and Texture of Colored Hair Treated with theBinding Formulation

General Three hair samples were obtained from a human subject and cut in½ inch wide wefts.

Coloring Formulation:

The permanent hair coloring formulation was obtained from a L'Oreal®permanent hair coloring service (L'Oreal® Majirel permanent color #10with 20 volume peroxide).

Binding Formulation:

A bismaleate binding agent,2,2′-(ethane-1,2-diylbis(oxy))bis(ethan-1-amine)di-maleate, at aconcentration of 300 mg in 10 g total solution (water) was used.

Methods

The hair samples were washed with a clarifying shampoo then towel dried.The samples were then colored with the L'Oreal® permanent hair colorservice, which was left on the hair samples for approximately 35-40minutes.

The first color treated hair sample (“control”) was subsequently rinsedand washed with Liqwd® Hydrating Shampoo and Conditioner five timesbefore being photographed.

The binding formulation was applied to the second and third colortreated hair samples via a spray bottle and massaging using the fingers.The binding formulation was left on the second hair sample for a periodof about 1 minute and on the third sample for a period of about 10minutes. The hair samples were subsequently rinsed, and then washed withLiqwd® Hydrating Shampoo and Conditioner five times before beingexamined.

Results:

The hair samples treated with the binding formulation showed bettercolor retention, more shine, and less frizz than the control. The hairsamples treated with the binding formulation felt smoother to the touchand combined with the lower frizz and added sheen gave an overallhealthier appearance over the control.

Example 7 Comparison of Color Retention in Traditionally Permed Hair andHair Permed Using the Binding Formulations

Method

A ½ inch wide weft of hair sample, obtained from a human subject, waswashed with clarifying shampoo then towel dried. Ammonium thioglycolateor dithiothreitol was mechanically pulled through the hair with a wideand a fine toothcomb several times then left on the hair for 10 minutesto 1 hour. The hair was then rinsed for 30 seconds to 1 minute withwater, and then towel dried.

The binding formulation, described in Example 1, was then applied via aneedle nose applicator drenching the hair and leaving it on for 7.5minutes. This step was repeated, for a total of 15 minutes. The hair wasthen rinsed for 1-2 minutes, shampooed, and then conditioned withvarious salon shampoo and conditioner brands, including LiQWd® HydratingShampoo and Hydrating Conditioner.

A second sample of hair was straightened, as described above, but usinghydrogen peroxide instead of the binding formulation. The hair sampleswere washed and conditioned repeatedly.

Comparison of Hair Color:

After both hair samples were washed five times using LiQWd® HydratingShampoo and LiQWd® Hydrating Conditioner, the samples were examined fortheir color retention.

Results

The hair sample treated with the binding formulation displayed a colorcloser in intensity to the hair sample prior to the first washing,compared to the hair treated with hydrogen peroxide.

Example 8 Comparison of Hair Treated with Highlighting FormulationApplied Simultaneously with Binding Formulation and Hair Treated withHighlighting Formulation Alone

The binding formulation in Example 1 contained the bismaleate bindingagent at concentrations of 2400 mg in 10 g total solution (water).

Two swatches of human hair were tested. A sample was taken from the samehead, 1 inch wide, and split in half. The color was medium brown and hadbeen previously color treated with an unknown professional hair color.

Swatch 1, ½ inch wide and 8 inches long, was lightened with traditionalhighlighting ingredients mixed with a binding formulation. 1 oz of JoicoVerocolor Veroxide developer-20 volume was mixed with 1 oz JoicoVerolight powder bleach to form the highlighting formulation. Then 9 mLof the binding formulation was added to the highlighting formulation toform a mixture.

The mixture was applied on the Swatch 1 hair with an applicator brush asthe hair lay on aluminum foil. The foil was then wrapped around theswatch and allowed to process for 35 minutes. The swatch was rinsed andshampooed one time.

Swatch 2, the control, ½ inch wide and 8 inches long, was lightened withtraditional highlighting ingredients in the absence of a bindingformulation. 1 oz of Joico Verocolor Veroxide developer-20 volume wasmixed with 1 oz Joico Verolight powder bleach to form a highlightingformulation with a creamy consistency.

The highlighting formulation was applied on the Swatch 2 hair with anapplicator brush as the hair lay on aluminum foil. The foil was thenwrapped around the swatch and allowed to process for 35 minutes. Theswatch was rinsed and shampooed one time.

Results

A noticeable difference in hair quality between Swatch 1 and Swatch 2was observed. Swatch 1 hair was softer, less frizzy, appeared hydrated,with more shine than the control, Swatch 2.

Both swatches were washed and conditioned 5 more times with the samenoticeable benefits of Swatch 1 (treated with the mixture ofhighlighting formulation and binding formulation) compared to thecontrol, Swatch 2 (treated with highlighting formulation, alone).

Unless defined otherwise, all technical and scientific terms used hereinhave the same meanings as commonly understood by one of skill in the artto which the disclosed invention belongs. Publications cited herein andthe materials for which they are cited are specifically incorporated byreference.

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, many equivalents to the specificembodiments of the invention described herein. Such equivalents areintended to be encompassed by the following claims.

1-30. (canceled)
 31. A kit comprising: (a) a first formulationcomprising a coloring or bleaching agent, and (b) a second formulationcomprising a binding agent of Formula I

wherein A, B, C, and D are reactive moieties capable of reacting withfree thiol groups in hair and contain one or more charges, and whereineach of A, B, C, and D independently contains a moiety selected from thegroup consisting of a vinyl sulfone, an acrylate, a methacrylate, astyrene group, an acryl amide group, a methacryl amide group, a maleategroup, a fumarate group, and an itaconate group; R is a linker thatcontains two or more charges, wherein the charges are opposite to thecharges on the reactive moieties, wherein n=1-10, and wherein R is not apolymer, and wherein the sum of the charges is zero; and wherein thereactive moieties are ionically bound to the linker; wherein eachoccurrence of p, q, r, and s is independently an integer from 0 to 25,and wherein the sum of p+q+r+s is equal to or greater than 2 in aneffective amount to covalently bind free thiol groups in hair.
 32. Thekit of claim 31, wherein the second formulation is in the form of aliquid.
 33. The kit of claim 31, wherein the second formulation is inthe form of a cream.
 34. The kit of claim 31, wherein the secondformulation is in the form of a lotion.
 35. The kit of claim 31, whereinthe second formulation is in the form of a milk.
 36. The kit of claim31, wherein the second formulation is in the form of a mousse.
 37. Thekit of claim 31, wherein the second formulation is in the form of aspray.
 38. The kit of claim 31, wherein the second formulation is in theform of a gel.
 39. The kit of claim 31, wherein the second formulationis in the form of a shampoo.
 40. The kit of claim 31, wherein the secondformulation is in the form of a conditioner.
 41. The kit of claim 31,wherein A, B, C, and D are the same.
 42. The kit of claim 31, wherein atleast one of A, B, C, and D is different than the other reactivemoieties.
 43. The kit of claim 31, wherein the linker is apolyfunctional molecule, wherein the linker is optionally independentlysubstituted with one or more substituents selected from the groupconsisting of hydrogen, halogen, cyano, alkoxy, alkyl, alkenyl,cycloalkyl, cycloalkenyl, aryl, heterocycloalkyl, heteroaryl, amine,hydroxy, formyl, acyl, carboxylic acid (—COOH), —C(O)R¹, —C(O)OR¹,carboxylate (—COO⁻), primary amide, secondary amide, —C(O)NR¹R², —NR¹R²,—NR¹S(O)₂R², —NR¹C(O)R², —S(O)₂R², —SR¹, and —S(O)₂NR¹R², sulfinylgroup, and sulfonyl group; wherein R¹ and R² may each independently behydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocycloalkyland heteroaryl; wherein each of R¹ and R² is optionally independentlysubstituted with one or more substituents selected from the groupconsisting of halogen, hydroxyl, cyano, nitro, amino, alkylamino,dialkylamino, alkyl optionally substituted with one or more halogen oralkoxy or aryloxy, aryl optionally substituted with one or more halogenor alkoxy or alkyl or trihaloalkyl, heterocycloalkyl optionallysubstituted with aryl or heteroaryl or ═O or alkyl optionallysubstituted with hydroxyl, cycloalkyl optionally substituted withhydroxyl, heteroaryl optionally substituted with one or more halogen oralkoxy or alkyl or trihaloalkyl, haloalkyl, hydroxyalkyl, carboxy,alkoxy, aryloxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, anddialkylaminocarbonyl.
 44. The kit of claim 31, wherein the binding agentis:


45. The kit of claim 31, wherein the second formulation furthercomprises one or more pharmaceutically acceptable excipients selectedfrom the group consisting of water, surfactants, vitamins, naturalextracts, preservatives, chelating agents, perfumes, preservatives,antioxidants, chelating agents, hair coloring agents, proteins, aminoacids, humectants, fragrances, emollients, penetrants, thickeners,viscosity modifiers, hair fixatives, film formers, emulsifiers,opacifying agents, propellants, liquid vehicles, carriers, salts, pHadjusting agents, neutralizing agents, buffers, hair conditioningagents, anti-static agents, anti-frizz agents, anti-dandruff agents, andcombinations thereof.
 46. The kit of claim 31, wherein the binding agentis present in an amount ranging from about 0.01 wt % to about 50 wt % ofthe second formulation.
 47. The kit of claim 45, wherein thepharmaceutical excipient is present in an amount ranging from about 10wt % to about 90 wt % of the second formulation.
 48. The kit of claim31, wherein the first and second formulations are pre-mixed.
 49. The kitof claim 31, further comprising a shampoo, a conditioner, instructionsfor use, a developer, mixing container, an odor eliminator, anapplicator, or a combination thereof.
 50. The kit of claim 37, whereinthe second formulation is provided as two or more separate ingredients.51. The kit of claim 44, wherein the binding agent is provided as a drypowder in a sealed package and the pharmaceutically acceptable excipientprovided in a vial or other container.
 52. The kit of claim 31, wherein:(1) the first formulation is a bleaching formulation comprising thebleaching agent; and (2) the binding agent of the second formulation isselected from:

and wherein the second formulation is in the form of a liquid or acream.
 53. The kit of claim 52, wherein the first and secondformulations are pre-mixed.
 54. The kit of claim 52, wherein thebleaching formulation further comprises a developer.
 55. The kit ofclaim 52, further comprising a shampoo, a conditioner, instructions foruse, a developer, mixing container, an odor eliminator, an applicator,or a combination thereof.
 56. The kit of claim 31, wherein: (1) thefirst formulation is a coloring formulation comprising the coloringagent; and (2) the binding agent of the second formulation is selectedfrom:

and wherein the second formulation is in the form of a liquid or acream.
 57. The kit of claim 56, wherein the first and secondformulations are pre-mixed.
 58. The kit of claim 56, further comprisinga shampoo, a conditioner, instructions for use, a developer, mixingcontainer, an odor eliminator, an applicator, or a combination thereof.